U.S. patent number 5,041,494 [Application Number 07/264,300] was granted by the patent office on 1991-08-20 for aqueous solutions or dispersions of polyurethanes, a process for their preparation and their use in coating compositions.
This patent grant is currently assigned to Bayer Aktiengesellschaft. Invention is credited to Joachim Franke, Hanns P. Muller.
United States Patent |
5,041,494 |
Franke , et al. |
August 20, 1991 |
Aqueous solutions or dispersions of polyurethanes, a process for
their preparation and their use in coating compositions
Abstract
The present invention is directed to aqueous solutions or
dispersions of cationically modified polyurethanes, characterized
in that the dissolved or dispersed polyurethanes (i) contain about
2 to 200 milliequivalents of incorporated ammonium groups per 100 g
of solids content, (ii) contain 0 to about 25% by weight of
ethylene oxide units within terminal or lateral polyether chains
and (iii) contain at least 1.3% by weight, calculated as SiO.sub.3
(molecular weight=76), of built-in structural units corresponding
to the formula ##STR1## wherein R', R" and R"' may be the same or
different and represent hydrogen or alkyl groups containing 1 to 4
carbon atoms, the total quantity of hydrophilic structural units
(i) and (ii) being sufficient to ensure the solubility or
dispersibility of the polyurethanes in water and the solutions or
dispersions having a pH value of 3 to 6. The present invention is
also directed to a process for the preparation of these storage
stable aqueous solutions or dispersions and to their use as coating
compounds or for the preparation of coating compositions for any
substrates.
Inventors: |
Franke; Joachim (Cologne,
DE), Muller; Hanns P. (Bergisch Gladbach,
DE) |
Assignee: |
Bayer Aktiengesellschaft
(Leverkusen, DE)
|
Family
ID: |
6339668 |
Appl.
No.: |
07/264,300 |
Filed: |
October 28, 1988 |
Foreign Application Priority Data
Current U.S.
Class: |
524/588; 528/28;
524/838 |
Current CPC
Class: |
C08G
18/0814 (20130101); C08G 18/283 (20130101); C08G
18/832 (20130101); C08G 18/10 (20130101); C08G
18/3893 (20130101); C08G 18/289 (20130101); C08G
18/10 (20130101); C08G 18/289 (20130101); C08G
18/10 (20130101); C08G 18/3893 (20130101) |
Current International
Class: |
C08G
18/00 (20060101); C08G 18/10 (20060101); C08G
18/28 (20060101); C08G 18/38 (20060101); C08G
18/83 (20060101); C08G 18/08 (20060101); C08L
083/04 () |
Field of
Search: |
;524/588,838
;528/28 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Kight, III; John
Assistant Examiner: Daley; Dennis R.
Attorney, Agent or Firm: Gil; Joseph C. Roy; Thomas W.
Claims
What is claimed:
1. A aqueous solution or dispersion having improved storage
stability and a pH value of 3 to 6 of a cationically modified
polyurethane which dries to form a cross-linked coating, said
polyurethane comprising
(i) about 2 to 200 milliequivalents of incorporated ammonium groups
per 100 g of solids content,
(ii) 0 to about 25% by weight of ethylene oxide units contained
within lateral or terminal polyether chains and
(iii) at least 1.3% by weight, calculated as SiO.sub.3, of
incorporated structural units corresponding to the formula
##STR12## wherein R', R" and R'" may be the same or different and
represent hydrogen or an alkyl group with 1 to 4 carbon atoms,
the hydrophilic structural units (i) and (ii) being present in a
quantity sufficient to ensure the solubility or dispersibility of
said polyurethane in water.
2. A process for the production of a coated substrate which
comprises coating said substrate with a coating composition
comprising the solution or dispersion of claim 1 and subsequently
curing said coating.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to new, storage stable aqueous solutions or
dispersions of polyurethanes containing alkoxysilane groups which
dry to form cross-linked films, to a process for their preparation
and to their use as coating compounds or for the preparation of
coating compositions for any substrates.
2. Description of the Prior Art
Polyurethanes containing alkoxysilane groups have already been used
in the form of their organic solutions for the preparation of
moisture hardening coatings (see e.g. EP-A-158,893 or U.S. Pat. No.
4,222,925). One serious disadvantage of these systems is the use of
organic solvents with the attendant disadvantages of environmental
pollution, combustibility and odor. Another disadvantage lies in
the sensitivity of these solutions to moisture. Even slight traces
of water may cause instant cross-linking or gelling which renders
the solution unusable.
In spite of the great sensitivity of the alkoxysilane groups to
traces of water, there has been no lack of attempts to prepare
polyurethanes containing alkoxysilane groups in the form of aqueous
solutions or dispersions which can be used as environmentally safer
coating compounds. EP-A-163,214, for example, describes aqueous
dispersions of polyurethanes containing organosilane groups but it
is pointed out in this prior publication that if the "silyl
concentration" in the polymer is greater than 0.1% by weight there
is a risk of premature gelling which is countered by keeping the pH
of the dispersion above 7. Such a low concentration of
cross-linkable centers is hardly suitable for ensuring the high
cross-link density essential for the production of high quality
surface coats and adjustment of the pH to values above 7 as
recommended in the prior publication obviously renders the
described dispersions unsuitable for the preparation of coatings
which harden spontaneously at room temperature.
The disclosure of U.S. Pat. No. 3,983,291 and especially of U.S.
Pat. No. 3,941,733 confirms this teaching of the prior art. In U.S.
Pat. No. 3,941,733, for example, it is stated that the compounds
are at their most stable at pH values of 6.5 to 9 and that curing
of the surface structures prepared from the dispersions is
preferably carried out under stoving conditions. It is obviously on
account of the problems of stability which are recognized by the
authors of U.S. Pat. No. 3,941,733 that the proportion of
cross-linkable siloxane groups is kept very low in the specific
polymers described in the examples. A low proportion of these
groups not only results in a low cross-linking density, as already
mentioned, but also means that stoving of the coatings is essential
if cross-linking is to be achieved to any significant extent with
the small amount of cross-linkable groups present.
It was therefore an object of the present invention to provide new
solutions or dispersions of polyurethanes containing cross-linkable
alkoxysilane groups which would be free from the above-mentioned
disadvantages of the systems known in the art. The new solutions
and dispersions should in particular be stable in storage and
contain a high concentration of cross-linkable alkoxysilane groups
so that they may be used for the production of high quality surface
structures which will undergo cross-linking at room
temperature.
It was surprisingly found that this problem could be solved by
providing the solutions or dispersions according to the invention
described below and the process for their preparation. Contrary to
the teaching in the state of the art cited above, the solutions and
dispersions according to the invention combine a high concentration
of cross-linkable alkoxysilane groups with very high storage
stability at pH values of 3 to 6 and enable high quality coatings
to be obtained which will harden at room temperature.
SUMMARY OF THE INVENTION
The present invention is directed to aqueous solutions or
dispersions of cationically modified polyurethanes, characterized
in that the dissolved or dispersed polyurethanes
(i) contain about 2 to 200 milliequivalents of incorporated
ammonium groups per 100 g of solids content,
(ii) contain 0 to about 25% by weight of ethylene oxide units
within terminal or lateral polyether chains and
(iii) contain at least 1.3% by weight, calculated as SiO.sub.3
(molecular weight=76), of built-in structural units corresponding
to the formula ##STR2## wherein R', R" and R'" may be the same or
different and represent hydrogen or alkyl groups containing 1 to 4
carbon atoms,
the total quantity of hydrophilic structural units (i) and (ii)
being sufficient to ensure the solubility or dispersibility of the
polyurethanes in water and the solutions or dispersions having a pH
value of 3 to 6.
The present invention is also directed to a process for the
preparation of storage stable aqueous solutions or dispersions of
cationically modified polyurethanes by the step or prepolymer
process wherein the improvement is based on chemically
incorporating an organic compound corresponding to the formula
##STR3## wherein X represents an organic groups containing at least
one isocyanate reactive group and R.sup.iv, R.sup.v and R.sup.vi
may be the same or different and represent an alkyl group having 1
to 4 carbon atoms and
adding sufficient acid to the solutions or dispersions to obtain a
pH value of 3 to 6.
This invention also relates to the use of the solutions or
dispersions as coating compounds or for the preparation of coating
compositions for any substrates.
DETAILED DESCRIPTION OF THE INVENTION
The process for the preparation of the inventive solutions or
dispersions is based on the reaction of
(a) organic polyisocyanates with
(b) organic polyhydroxyl compounds in the molecular weight range of
400 to about 6000,
(c) compounds containing tertiary amine nitrogen atoms and at least
one isocyanate reactive group,
(d) organic compounds corresponding to the following general
formula ##STR4## wherein X represents an organic group carrying at
least one isocyanate reactive group and
R.sup.iv, R.sup.v and R.sup.vi may be the same or different and
represent alkyl groups having 1 to 4 carbon atoms,
(e) optionally compounds which are monofunctional or difunctional
in isocyanate addition reactions and contain a hydrophilic
polyether chain in which at least 40 mole-% of the chain members
are ethylene oxide units and
(f) optionally alcoholic, aminic and/or hydrazinic chain
lengthening agents in the molecular weight range of 32 to 399.
The reaction of component (a) with components (b) to (f) may be
carried out as a one-shot process, optionally in the presence of an
inert, water-miscible solvent, followed by conversion of the
polyurethane which is present in solution into an aqueous solution
or dispersion. Alternatively an isocyanate prepolymer is first
prepared from an excess quantity of component (a) and from
components (b), (c), (d) and optionally (e) which may be added in
any sequence or as mixtures, optionally in the presence of an
inert, water-miscible solvent. The isocyanate prepolymer is
subsequently mixed with water optionally containing aminic or
hydrazininc chain lengthening agents (f) and converted into an
aqueous solution or dispersion with concomitant chain
lengthening.
In either process the incorporated tertiary nitrogen atoms are
neutralized with an acid at the latest at the stage when the
prepolymer is dissolved or dispersed in water. The quantity of
acid, which is optionally used in excess, is calculated to result
in a solution or dispersion having a pH of 3 to 6. The nature and
proportions of the starting components are chosen so that the
polyurethanes present as solutions or dispersions contain
(i) about 2 to 200 milliequivalents of incorporated ammonium groups
per 100 g of solids content,
(ii) 0 to about 25% by weight of ethylene oxide units within
lateral or terminal polyether chains and
(iii) at least 1.3% by weight, calculated as SiO.sub.3 (molecular
weight=76) of incorporated structural units corresponding to the
following formula ##STR5##
Suitable polyisocyanates (a) include organic compounds containing
at least two free isocyanate groups. Diisocyanates of the formula
Q(NCO).sub.2 are preferably used wherein Q denotes an aliphatic
hydrocarbon groups with 4 to 12 carbon atoms, a cycloaliphatic
hydrocarbon group with 6 to 15 carbon atoms, an aromatic
hydrocarbon group with 6 to 15 carbon atoms or an araliphatic
hydrocarbon group with 7 to 15 carbon atoms.
Examples of preferred diisocyanates include tetramethylene
diisocyanate, hexamethylenediisocyanate,
dodecamethylenediisocyanate, 1,4-diisocyanatocyclohexane,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane,
4,4'-diisocyanato-dicyclohexylmethane,
4,4'-diisocyanato-2,2-dicyclohexylpropane, 1,4-diisocyanatobenzene,
2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene,
4,4'-diisocyanatodiphenylmehtane, m- and p-xylylenediisocyanate,
.alpha.,.alpha.,.alpha.',.alpha.'-tetramethyl-m- and
p-xylylenediisocyanate and mixtures of these compounds.
Known higher functional polyisocyanates and the known modified
polyisocyanates containing, for example, carbodiimide groups,
allophanate groups, isocyanurate groups, urethane groups and/or
biuret groups may, of course, also be included in limited
amounts.
Suitable starting materials (b) for the process according to the
invention include polyether, polyester, polyetherester,
polycarbonate and polyacrylate polyols in the molecular weight
range of 400 to about 6000, preferably about 500 to 3000. Mixtures
of such polyhydroxyl compounds may also be used. Examples of
suitable polyols are found in U.S. Pat. No. 4,305,858, herein
incorporated by reference. Polyether polyols or polyester polyols
in the above-mentioned molecular weight range containing (on
statistical average) 2 to 3, preferably 2, alcoholic hydroxyl
groups are preferably used as component (b). The preparation of
these starting materials is known in the art and has been
described, for example, in Kunststoff-Handbuch, Volume VII,
"Polyurethane", Carl Hanser Verlag, Munich (1966), pages 45 et
seq.
Starting components (c) include hydroxy-functional and/or
aminofunctional, monofunctional and especially bifunctional
compounds in the molecular weight range of 88 to about 1000,
preferably 89 to about 300 which contain tertiary amine nitrogen
atoms. The nitrogen atoms may be converted at least partly into
tertiary or quaternary ammonium groups by neutralization or
quaternization during or after termination of the isocyanate
polyaddition reaction. Examples include
2-(N,N-dimethylamino)-ethylamine, N-methyl-diethanolamine,
N-methyl-diisopropanolamine, N-ethyl-diethanolamine,
N-ethyl-diisopropanolamine,
N,N'-bis-(2-hydroxyethyl)-perhydropyrazine,
N-methyl-bis-(3-aminopropyl)-amine,
N-methyl-bis-(2-aminoethyl)-amine,
N,N',N"-trimethyl-diethylenetriamine, N,N-dimethyl-aminoethanol,
N,N-diethyl-aminoethanol, 1-(N,N-diethylamino)-2-aminoethane and
1-(N,N-diethylamino)-3-aminopropane.
The starting components d) to be used according to the invention
include compounds corresponding to the formula ##STR6## in which
R.sup.iv, R.sup.v, and R.sup.vi may be the same or different and
represent alkyl groups having 1 to 4 carbon atoms, preferably
methyl or ethyl groups and
X represents an organic group containing at least one isocyanate
reactive group, preferably a hydroxyl or primary amino group, as
substituent.
Particularly suitable compounds (d) of this type include those
corresponding to the formula wherein R.sup.iv, R.sup.v and R.sup.vi
represent methyl or ethyl groups and X represents 2-hydroxyethyl,
3-hydroxypropyl, 2-(2-hydroxy)-ethyl, 2-(2-aminoethylamino)-ethyl
or 3-(3-aminopropylamino)-propyl group.
The following are examples of preferred suitable starting materials
(d): H.sub.2 N--(CH.sub.2).sub.3 --Si(O--CH.sub.2 --CH.sub.3
.sub.3, HO--CH(CH.sub.3)--CH.sub.2 --Si(OCH.sub.3).sub.3,
HO--(CH.sub.2).sub.3 --Si(OCH.sub.3).sub.3, HO--CH.sub.2 --CH.sub.2
--O--CH.sub.2 --CH.sub.2 --Si(OCH.sub.3).sub.3, (HO--C.sub.2
H.sub.5).sub.2 --N--(CH.sub.2).sub.3 --Si(OCH.sub.3).sub.3,
HO--(C.sub.2 --H.sub.4 --O).sub.3 --C.sub.2 H.sub.4
--N(CH.sub.3)--(CH.sub.2).sub.3 --Si(O--C.sub.4 H.sub.9).sub.3,
H.sub.2 N--CH.sub.2 --C.sub.6 H.sub.4 --CH.sub.2 --CH.sub.2
--Si(OCH.sub.3).sub.3, HS--(CH.sub.2).sub.3 --Si(OCH.sub.3).sub.3,
H.sub.2 N--(CH.sub.2).sub.3 --NH--(CH.sub.2).sub.3
--Si(OCH.sub.3).sub.3, H.sub.2 N--CH.sub.2 --CH.sub.2
--NH--(CH.sub.2).sub.2 --Si(OCH.sub.3).sub.3, H.sub.2
N--(CH.sub.2).sub.2 -- NH--(CH.sub.2).sub.3
--Si(OCH.sub.3).sub.3.
Optional starting material (e) include organic compounds in the
molecular weight range of about 800 to 10,000, preferably about
1000 to 5000, which contain one or two hydroxyl groups and a
polyether chain. The polyether chain is a lateral chain in the case
of divalent polyether alcohols. The polyether chains in these
compounds are based on at least 40 mole-%, preferably at least 65
mole-% of ethylene oxide units, the remainder being other alkylene
oxide units, preferably propylene oxide units.
Examples of suitable starting components (e) include the
hydrophilic starting components containing polyether chains and
hydroxyl groups disclosed in U.S. Pat. No. 4,237,264, U.S. Pat. No.
4,092,286 and U.S. Pat. No. 4,190,566, the disclosures of which are
herein incorporated by reference.
The optional starting components (e) are preferably monohydric
polyether alcohols in the abovementioned molecular weight range
which may be obtained by the alkoxylation of monovalent starting
molecules such as methanol, ethanol or preferably n-butanol with
ethylene oxide or mixtures of ethylene oxide and preferably
propylene oxide as alkoxylating agents.
Optional starting components f) include organic, preferably
divalent and/or trivalent, more preferably divalent polyhydroxyl
compounds in the molecular weight range of 62 to 399, preferably
from 62 to about 250, or aminic or hydrazinic chain lengthening
agents or cross-linking agents in the molecular weight range of 32
to 399, preferably 60 to about 250.
Examples of polyhydroxyl compounds include monohydric alcohols such
as ethylene glycol, propylene glycol, propane-1,3-diol,
butane-1,4-diol, hexane-1,6-diol, trimethylolpropane and glycerol.
Low molecular weight polyester diols such as the
bis-(hydroxyethyl)ester of adipic acid or low molecular weight
diols containing ether groups such as diethylene glycol,
triethylene glycol, tetraethylene glycol, dipropylene glycol,
tripropylene glycol or tetrapropylene glycol may also be used as
starting component e).
Compounds containing reactive NH groups include ethylenediamine,
hexamethylenediamine, piperazine, 2,5-dimethylpiperazine,
1-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophorone
diamine, IPDA), 4,4'-diamino-dicyclohexylmethane,
1,4-diamino-cyclohexane, 1,2-diamino-propane, hydrazine, hydrazine
hydrate, amino-acidhydrazides such as 2-aminoacetic acid hydrazide
and bis-hydrazides such as succinic acid-bis-hydrazide.
The aminic and hydrazinic chain lengthening agents in particular,
which contain no tertiary nitrogen atoms, may also be used in
blocked form in the process according to the invention, i.e. in the
form of the corresponding ketimines (DE-AS 2,725,589), ketazines
(DE-OS 2,811,148, U.S. Pat. No. 4,269,748) or amine salts (U.S.
Pat. No. 4,292,226). Oxazolidines of the type used, for example, in
DE-OS 2,732,131 or U.S. Pat. No. 4,192,937 are also masked diamines
which may be used for chain lengthening the isocyanate prepolymers.
When such masked diamines are used, they are generally mixed with
the isocyanate prepolymers in the absence of water and the mixture
obtained is subsequently mixed with the water of dispersion or with
part of the water of dispersion so that the corresponding diamines
are released as intermediate products by hydrolysis.
Further examples of compounds to be used as starting components f)
in the process according to the invention are described, for
example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and
Technology", by Saunders-Frisch, Interscience publishers, New York,
London, Volume I, 1962, pages 32 and 42 and pages 44 to 54 and
Volume II, 1964, pages 5 to 6 and 198 to 199 and in
Kunststoff-Handbuch, Volume VII, Vieweg-Hochtlen,
Carl-Hanser-Verlag, Munich 1966, e.g. on pages 45 to 71.
Isocyanate reactive compounds which are trifunctional or higher
functional in isocyanate polyaddition reactions may be included in
small amounts to produce a certain degree of branching as discussed
with the previously mentioned trifunctional or higher functional
polyisocyanates. Monohydric alcohols, e.g. n-butanol, n-dodecanol
or stearyl alcohol, may also be used in small quantities.
In the process according to the invention, the ammonium groups are
incorporated by means of starting components (c) containing
tertiary amino groups, the tertiary amino groups being converted
into the corresponding ammonium groups by neutralization with
inorganic or organic acids such as hydrochloric acid, acetic acid,
fumaric acid, maleic acid, lactic acid, tartaric acid, oxalic acid
or phosphoric acid.
The quantity of starting component (c) and the quantity of acid
used for neutralization are calculated so that the polyurethanes
contain about 2 to 200 milliequivalents, preferably about 2 to 100
and most preferably about 5 to 50 milliequivalents of ammonium
groups per 100 g of solids content and the solutions or dispersions
have a pH of 3 to 6. This means that the acid is frequently used in
excess, based on the tertiary nitrogen atoms in component (c),
especially when weak acids are used.
In addition to the ammonium groups, the polyurethanes may contain
hydrophilic polyether segments. The quantity of such polyether
chains incorporated in lateral or terminal positions corresponds to
a quantity of ethylene oxide units incorporated in the polyether
chains of the polyurethanes of up to about 25% by weight,
preferably up to about 10% by weight, based on the total weight of
the polyurethane. In any case, the total quantity of ammonium
groups and hydrophilic polyether chains must be selected to ensure
that the polyurethanes will be soluble or dispersible in water.
Preferably, starting components (e) are not used and the necessary
hydrophilic character is ensured by the incorporation of ammonium
groups.
The starting components (d) are used in such a quantity in the
process according to the invention that the resulting polyurethanes
contain at least 1.3% by weight, preferably 1.3 to about 8% by
weight (calculated as SiO.sub.3, molecular weight=76) of SiO.sub.3
units incorporated in the form of structural units corresponding to
the formula ##STR7## These incorporated structural units
correspond, of course, to the starting component (d) although the
possibility of partial hydrolysis of the alkoxysilane groups by the
water used as solvent or dispersing agent with the formation of
hydroxysilane groups cannot be excluded.
The optional starting component (f) for the process according the
invention are used, if at all, in quantities of up to about 10% by
weight, preferably up to about 5% by weight, based on the weight of
component b).
In the process according to the invention, it is preferable first
to prepare a prepolymer containing free isocyanate groups from
starting components (a) and (b) in the presence of an inert solvent
(such as acetone or N-methylpyrrolidone) or in the absence of
solvent. Components (c) and optionally (e) may also be added at
this stage or after prepolymer formation. These components are
reacted together in such proportions that an NCO/OH equivalent
ratio of about 1.2:1 to 2.5:1, preferably about 1.2:1 to 2:1 is
maintained. The reaction temperature employed is generally about 5
to 160.degree. C., preferably about 50.degree. to 100.degree.
C.
The isocyanate prepolymer obtained is then converted into the high
molecular weight products by a reaction with component (d),
optionally (c) and/or optionally (f).
The components are used in quantities corresponding to an
equivalent ratio of isocyanate groups in the prepolymer to
isocyanate reactive groups in components (d), (c) and (f) of about
0.8:1 to 2.5:1, preferably about 0.8:1 to 2:1. The chain
lengthening reaction (reaction with component f)) may be carried
out by any of several different variations. For example, the
isocyanate prepolymer may be reacted with component (d) and at the
same time with component (f) in an inert solvent such as acetone or
N-methylpyrrolidone. The resulting organic solution may then by
mixed with water and the solvent may subsequently be removed by
distillation. In another variation, the isocyanate prepolymer may
first be reacted with a sub-equivalent quantity of component (d),
based on the quantity of isocyanate groups, in a solvent of the
type mentioned above to form an isocyanate prepolymer containing
alkoxysilane groups and this prepolymer may then be mixed with
blocked chain lengthening agents of the type mentioned above and
this mixture may then be dispersed in water. In the first mentioned
variation, introduction of the ammonium groups may be carried out,
for example, by neutralization of the tertiary amino groups before
the addition of water or by using an aqueous solution of the acid
as neutralizing agent. According to the second variation, for
example, the acid required for neutralizing the tertiary amino
groups may be added to the water of dispersion. Another variation
of the process according to the invention consists of a single
stage reaction of components (a), (b), (c) and (d) and optionally
(e) and (f) in an organic solvent of the type mentioned above at
about 20.degree. to 80.degree. C. and conversion of the dissolved
polyurethane into an aqueous dispersion, preferably using aqueous
solutions of the required acid, optionally followed by distillative
removal of the solvent.
The reaction of the isocyanate prepolymers with components (d) and
optionally (c) or (f) and the dispersion of the prepolymer in water
are generally carried out within the temperature range of about
20.degree. to 100.degree. C., preferably about 20.degree. to
80.degree. C. The quantity of water is generally calculated to
result in about 10 to 60% by weight, preferably about 20 to 50% by
weight solutions or dispersions of the polyurethanes.
The procedure for preparing the solutions or dispersions according
to the invention is not limited to the process according to the
invention, which is merely a preferred method of obtaining the
products according to the invention. The tertiary amino groups
present in the isocyanate prepolymers, for example, could equally
be first at least partially converted into ammonium groups by
quaternization, and instead of using starting component (c)
containing tertiary amine nitrogen atoms, starting components
already containing ammonium groups could be used for the
preparation of the isocyanate prepolymers. The end products will
again be polyurethanes conforming to the particulars given above
concerning the ammonium groups content. The term "ammonium groups"
therefore stands both for tertiary ammonium groups obtained by the
neutralization of the tertiary amine with an acid and for
quaternary ammonium groups obtained by alkylation of a tertiary
amino group.
The aqueous solutions or dispersions according to the invention
could in principle also be prepared by procedures analogous to the
so-called melt dispersion process of U.S. Pat. No. 3,756,922 or the
method according to DE-OS 2,543,091.
The solutions or dispersions of polyisocyanate polyaddition
compounds according to the invention may be directly used as such
for coating any organic or inorganic substrates. The dispersions
may be applied to the substrate either directly or after dilution.
As the lacquers dry, the alkoxysilane and hydroxysilane groups
cross-link by known reactions: ##STR8## to form siloxane groups. As
already mentioned above, the reaction according to equation (1) at
least partly takes place in the solution or dispersion according to
the invention. However, the storage stability of the solutions and
dispersions according to the invention is evidently due to the fact
that reaction (2) which leads to cross-linking does not take place
or only to an insignificant extent in the presence of the excess
water.
The cross-linking reaction generally proceeds sufficiently rapidly
at room temperature, i.e. within a period of less than 24 hours.
Drying and cross-linking of the films may be accelerated by stoving
the applied films at an elevated temperature, i.e. in the range of
about 25.degree. to 150.degree. C., preferably about 80.degree. to
130.degree. C.
The coatings obtained are hard, elastic, extremely solvent
resistant and may be either clear or matte, depending on the
starting materials used.
The substrates for the PUR dispersion according to the invention
may be any organic or inorganic materials, e.g. glass (including
glasses and glass panels, glass fibers and glass bottles), wood and
wood-like products, metals, plastics, leather, paper, building
materials, stone and rock.
Another advantage is that the dispersions according to the
invention can be deposited on metallic substrate by
cataphoresis.
The usual auxiliary agents and additives known from lacquer
technology may, of course, be added when the products are used
according to the invention. Auxiliary agents and additives such as
pigments, viscosity regulating substances, anti-foamants, UV
absorbents, anti-oxidants and other substances which prevent
polymer degradation (such as sterically hindered amines), etc. may
also be used.
Application of the lacquers is carried out by the conventional
methods of lacquer technology such as spraying, casting, immersion
or roller coating. The lacquers are generally applied in quantities
resulting in dry film thicknesses of about 0.005 to 0.10 mm.
In the following examples, all percentages are percentages by
weight.
EXAMPLES
General method for the preparation of the cationic PUR
dispersions
(a) Preparation of the prepolymer
The relatively high molecular weight polyhydroxyl compound (b) and
optionally the hydrophilic polyether component (e) were introduced
into a dry three-necked flask and dehydrated under a vacuum at
120.degree. C. for one hour. The polyisocyanate component (a) was
then introduced under nitrogen into the melt which had cooled to
80.degree. C.
The mixture was stirred at 80.degree. C. until the isocyanate
content determined by titration had decreased to the theoretically
calculated isocyanate content.
The mixture was then diluted to a solids concentration of about 50%
with anhydrous acetone and stabilized with benzoyl chloride added
in a quantity of 0.5%, based on the polymer.
(b) Chain lengthening and dispersion
The organosilanes (d) and the compounds (c) containing cationic or
potential cationic groups were introduced into the reaction vessel
as an approximately 20 to 50% solution in acetone and the
prepolymer described under (a) was added dropwise at a temperature
<40.degree. C.
The mixture was then stirred at room temperature or at an elevated
temperature of up to about 70.degree. C. until no more isocyanate
could be detected by IR spectrometry. The mixture was then
neutralized with acid and the dispersing water was added. The
acetone was removed in a water jet vacuum.
A stable, finely divided aqueous dispersion which was stable in
storage under these conditions was obtained.
TABLE
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Compound Iso- Macro- (c) with Organo- Poly- Concen- SiO.sub.3 Ex-
cyanate diol dispersing silane ether Water tration content ample
(a) [g] (b) [g] action [g] (d) [g] (e) [g] Acid [g] [g] [%] [%] pH
__________________________________________________________________________
1 1 444 1 1700 1 72.5 1 221 -- 1 90 7630 24 3.12 3.25 2 1 444 1
1700 1 108.8 1 110.5 -- 1 300 5777 28 1.61 3.80 3 1 555 1 1700 1
145 1 221 -- 1 300 8475 23 2.90 4.00 4 1 444 1 1700 1 72.5 2 222 --
1 300 6405 29 3.12 4.07 5 1 444 1 1700 1 72.5 2 111 -- 1 300 5685
28 1.63 3.67 6 1 444 2 2250 1 72.5 1 221 -- 1 300 6050 32 2.54 3.80
7 1 444 2 2250 1 108.8 1 110.5 -- 1 300 4879 36 1.30 4.00 8 1 444 2
2250 1 72.5 2 222 -- 1 300 10295 22 2.54 4.60 9 1 444 2 2250 2 89.2
1 110.5 -- 1 300 6140 31 1.31 3.64 10 2 500 2 2250 1 116 1 144 200
1 200 3141 49 1.54 3.75 11 2 500 2 2250 2 95.2 1 144 200 1 300 2833
50 1.66 3.78 12 1 331 3 432 1 72.5 1 221 -- 1 333 4480 18 7.19 3.47
13 1 369 3 511 1 72.5 1 221 -- 1 300 4700 19 6.47 3.77 14 1 369 3
511 1 72.5 1 221 100 1 100 2164 36 5.97 3.70 15 1 369 3 511 1 72.5
1 159 100 1 100 2810 30 4.38 4.48 16* 1 369 3 511 1 72.5 1 221 -- 2
210 4485 20 6.47 1.1 17* 1 369 3 511 1 72.5 1 221 -- 1 30 4385 21
6.47 7.1 18* 1 369 3 511 1 72.5 1 221 -- 1 25 4670 20 6.47 7.5 19 1
369 3 511 1 72.5 1 221 -- 3 450 4895 18 6.47 3.00 20* 1 369 3 511 1
72.5 1 221 -- 4 100 4903 19 6.47 1.5 21* 1 444 1 1700 4 95 1 221 --
-- -- 9840 20 3.09 10.8 22* 1 444 1 1700 5 67 1 221 -- -- -- 9150
21 3.13 8.9
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*Comparison Examples
DESCRIPTION OF THE POLYISOCYANATE (A) ##STR9##
DESCRIPTION OF THE POLYHYDROXYL COMPOUNDS (B)
No. 1: Polyester of adipic acid, hexanediol and neopentyl glycol
(molar ratio of diols 65:35) OH number=64-68
No. 2: Polyester of adipic acid and butanediol OH number=48-52
No. 3: Polyacrylate, OH number 140-150
DESCRIPTION OF THE (POTENTIAL) IONIC STARTING COMPONENT (C)
##STR10##
DESCRIPTION OF THE ORGANOSILANES (D) ##STR11##
DESCRIPTION OF THE HYDROPHILIC POLYETHER ALCOHOL (E)
A polyether started on butanol and prepared with a mixture of
63.5 mole-% of ethylene oxide units and
36.5 mole-% of propylene oxide units.
OH number approx. 25
DESCRIPTION OF THE ACIDS
No. 1: Acetic acid
No. 2: Dibutylphosphate
No. 3: Lactic acid
No. 4: 1M hydrochloric acid
Examples 16, 17, 18, 20, 21 and 22 are Comparison Examples as may
be seen from the pH values, which lie outside the range according
to the invention. The dispersions according to Examples 21 and 22
are anionically modified and in this respect also not according to
the invention. All the dispersions of the Comparison Examples have
a storage stability of less than one day at room temperature, which
is totally inadequate. The dispersions according to the invention
described in the Embodiment Examples are storage-stable products
which dry to form high quality, cross-linked coatings.
EXAMPLE 23 (USE)
The dispersion according to Example 13 was spread coated on a glass
plate and left to dry at room temperature for 24 hours. A hard but
elastic and scratch-resistant film with very high resistance to
water, dilute acetic acid, acetone, toluene and ethanol was
obtained. The drying time was reduced to 30 minutes by stoving at
120.degree. C. The film then obtained had the same advantageous
properties.
Although the invention has been described in detail in the
foregoing for the purpose of illustration, it is to be understood
that such detail is solely for that purpose and that variations can
be made therein by those skilled in the art without departing from
the spirit and scope of the invention except as it may be limited
by the claims.
* * * * *